Antraquinone dyestuffs

ABSTRACT

Reactive dyestuffs of the formula ##STR1## WHEREIN R 1 , R 2 , R 3 , X, Y and Z have the meaning given in the description and their use for the dyeing and printing of materials which contain hydroxyl groups and materials which contain N, such as cotton, wool and the like, by the customary processes.

The present invention relates to reactive dyestuffs to the generalformula ##STR2## wherein R₁ and R₂ = H or alkyl, especially C₁ -C₄-alkyl,

R₃ = h or a sulphonic acid group,

X = optionally substituted phenylene,

Y = co or SO₂ and

Z = phenylene.

Suitable radicals R₁ and R₂ are, in particular, hydrogen and methyl.Suitable phenylene radicals X are, for example, phenylene radicalssubstituted by sulpho and C₁ -C₄ -alkyl, such as ##STR3## Preferreddyestuffs are those of the following formula (II) ##STR4## wherein R₁and R₂ = H or alkyl,

R₄, r₅ and R₆ = H or alkyl,

R₇ = h or a sulphonic acid group,

Y = co or SO₂ and

Z = phenylene and

alkyl preferably represents C₁ -C₄ -alkyl.

The dyestuffs can be prepared, for example, by the following route:compounds of the formula (III) ##STR5## wherein

R₁, R₃ and X have the meaning indicated in formula (I), are reacted withcompounds of the formula (IV)

    w-y-z-no.sub.2                                             (iv)

wherein

W = a removable radical, especially halogen, such as Cl,

Br or F,

and wherein

Y and Z have the meaning indicated in formula (I), to give compounds ofthe formula (V) ##STR6## wherein

R, R₃, X, Y and Z have the meaning indicated in formula (I).

In the compounds of the formula (V), which are thus obtained, the nitrogroup is converted into an amino group in a suitable manner, for exampleby reduction with alkali metal salts of hydrogen sulphide or by means ofhydrazine, and compounds of the formula (VI) are thus obtained. ##STR7##

The compounds of the formula (VI) are then reacted with2,4,6-trifluoro-5-chloro-pyrimidine of the formula (VII) ##STR8## togive the desired dyestuffs of the formula (I), in which R₂ = hydrogen.

The conversions of (III) to (V), of (V) to (VI) and of (VI) to (I) arecarried out in water, optionally with the addition of acid amides, suchas caprolactam or dimethylformamide, or of ethers, such as dioxane. ThepH value can be varied from 11 to 4; the reactions are carried out in atemperature range of 0°-50° C.

Another embodiment consists in reacting compounds of the formula (VIII)##STR9## with compounds of the formula (IX) ##STR10## to give compoundsof the formula (X) ##STR11## wherein

R₁, R₂, R₃, X and Z have the meaning indicated in formula (I) and Acyldenotes an acid radical which can be split off easily, such as, forexample, the radical of formic acid, that is to say --CHO.

This radical is then split off and the compounds (XI) ##STR12## whichare thus obtained, are reacted with 2,4,6-trifluoro-5-chloro-pyrimidineof the formula (VII) to give dyestuffs of the formula (I), in which

R₁, r₂, r₃, x and Z have the meaning indicated in that formula and

Y = co.

the reactions of (VIII) with (IX) to give (X) are carried out insulphuric acid which is 90-100% pure, or in oleum which contains 0-20%of free SO₃. The temperature can be varied from 0°-30° C.

The conversions of (X) to (XI) are effected in dilute mineral acids,such as 1-10% strength hydrochloric acid or sulphuric acid, attemperatures of 20°-40° C.

A further embodiment consists in reacting compounds of the formula(VIII) with compounds of the formula (XII) ##STR13## to give compoundsof the formula (XIII) ##STR14## wherein

R₁, R₃, X and Z have the meaning indicated in formula (I). The reactionconditions are the same as those for the conversion of (VIII) to (X).Compounds of the type of the formula (V) wherein

Y = co,

are obtained in this way.

The further conversions are carried out analogously to the conversion of(V) to (VI) and, subsequently, to the reaction of (VI) with (VII) togive (I).

The dyestuffs which are thus obtained correspond to the formula (I),

wherein

R₁, r₃, x and Z have the meaning indicated in that formula and

R₂ = h and

Y = co.

particularly preferred dyestuffs are those of the formula (XIV)##STR15## and, amongst these, especially those of the formula (XV)##STR16## in which formulae Alkyl = C₁ -C₄ -alkyl. Examples of suitablecompounds of the formula (III) are ##STR17## Examples of suitablecompounds of the formula (IV) are ##STR18## Examples of suitablecompounds of the formula (VIII) are: ##STR19## Examples of suitablecompounds of the formula (IX) are: ##STR20## Examples of suitablecompounds of the formula (XII) are: ##STR21##

The new dyestuffs are suitable for dyeing and printing materials whichcontain hydroxyl groups and materials which contain N, such as cotton,wool and the like, by the customary processes.

The formulae given in the description are those of the free acids.Dyeing is generally carried out with the salts, especially the alkalimetal salts and preferably the sodium salts, potassium salts or lithiumsalts.

EXAMPLE 1

1.1 ##STR22##

25.85 parts (0.05 mol) of1-amino-4-(4'-methyl-2'-aminomethyl-anilino)-anthraquinone-2,6'-disulphonicacid are stirred in 260 parts of water at 20°-25° C and brought intosolution by adding about 8.5 parts of 50% strength sodium hydroxidesolution. The pH value should be 8-10. 10.2 parts of 4-nitrobenzoylchloride are added and the pH value is kept at 9-9.5 by adding 2 Nsodium hydroxide solution dropwise. When the reaction has ended, themixture is heated to 80°, in order to decompose the excess nitrobenzoylchloride which is still present, and is cooled to 20°-25° and theproduct is salted out with 16 parts of sodium chloride. The product,which has crystallised well, is filtered off, washed with 10% strengthsodium chloride solution and dried at 100°.

The starting material can be characterised by thin layer chromatography:DC-Alufolie Cellulose (aluminium foil/cellulose for thin layerchromatography) (Merck), ethyl acetate/pyridine/water, 14:5:4 (V/V/V)r_(F) value = 0.30.

1.2 ##STR23##

33.3 parts (0.05 mol) of the intermediate product obtained according to1.1, calculated as the free acid, are dissolved, in the form of thesalt-containing di-sodium salt, in 290 parts of water at 90° C. Anaqueous 18-20% strength solution of 2.95 parts (0.525 mol) of sodiumhydrogen sulphide is added dropwise at this temperature in the course of10 minutes, the mixture is cooled to 20°-25° C and 25 parts of sodiumchloride are added. After 2-3 hours, the crystals which have separatedout are filtered off, washed with 10% strength NaCl solution and driedat 100°.

1.3. ##STR24##

31.8 parts (0.05 mol) of the intermediate product obtained according to1.2., calculated as the free acid, are dissolved, in the form of thedi-sodium salt, in 340 parts of water at 60° C. The solution is cooledto 20°-25° C. 11.4 parts (0.068 mol) of2,4,6-trifluoro-5-chloro-pyrimidine are added and the pH value is keptat 6-7by adding 2 N sodium hydroxide solution dropwise. The dyestuffcrystallises immediately, without the addition of salt. It is filteredoff after several hours, washed with 5% strength sodium chloridesolution and dried at 60°.

A clear, reddish-tinged blue dyeing is obtained on wool.

It is possible to combine reactions 1.1. and 1.2. by not salting out theproduct from stage 1.1 but heating it, after the reaction has ended, to90° C, then adding sodium hydrogen sulphide solution dropwise, asdescribed for stage 1.2., and proceeding further as indicated in stage1.2.

The compounds which follow can also be prepared analogously to Example1:

    __________________________________________________________________________     ##STR25##                                                                                                          Colour shade on wool                    Example                                                                            R.sub.3                                                                             X           R.sub.1                                                                          Y  Z        or cotton                               __________________________________________________________________________    2    H                                                                                    ##STR26##  H  CO                                                                                ##STR27##                                                                             clear reddish-tinged blue               3    6-SO.sub.3 H                                                                         ##STR28##  H  CO                                                                                ##STR29##                                                                             greenish-tinged blue                    4    H                                                                                    ##STR30##  H  SO.sub.2                                                                          ##STR31##                                                                             clear reddish-tinged blue               5    H                                                                                    ##STR32##  H  CO                                                                                ##STR33##                                                                             neutral blue                            6    H                                                                                    ##STR34##  CH.sub.3                                                                         CO                                                                                ##STR35##                                                                             clear reddish-tinged blue               7    H                                                                                    ##STR36##  H  SO.sub.2                                                                          ##STR37##                                                                             clear reddish-tinged blue               8    5-SO.sub.3 H                                                                         ##STR38##  H  CO                                                                                ##STR39##                                                                             greenish-tinged blue                    9    H                                                                                    ##STR40##  CH.sub.3                                                                         CO                                                                                ##STR41##                                                                             clear reddish-tinged blue               10   H                                                                                    ##STR42##  H  CO                                                                                ##STR43##                                                                             clear reddish-tinged                    __________________________________________________________________________                                          blue                                

We claim:
 1. Reactive dyestuff of the formula ##STR44## wherein R₁, R₂and R₃ are hydrogen;X is phenylene or phenylene substituted with C₁ -c₄-alkyl, with or without one sulfo groups; Y is CO or SO₂ ; and Z isphenylene.
 2. Reactive dyestuff of the formula ##STR45## wherein R₁ andR₂ are H;R₄ is H or sulfo; R₅, r₆ and R₇ are H or C₁ -C₄ -alkyl; and Yis CO or SO₂.
 3. Reactive dyestuff of the formula ##STR46##
 4. Reactivedyestuff of the formula ##STR47##